1-(2-cyanoethoxy)-2,2-dichlorovinyl phosphate esters

ABSTRACT

Compound having the formula:   WHEREIN R is alkyl (C1-C4), haloalkyl (C1-C4), alkenyl (C2-C4), phenyl, alkylphenyl, or halophenyl, are new compounds that are useful as insecticides.

United States Patent 1 Gough in] 3,725,511 51" Apr. 3, 1-973 l -(2-CYANOETHOXY)-2 ,2-

DICHLOROVINYL PHOSPHATE 3,324,203 6/l967 Weesner 260/940 Primary Examiner- Lewis Gotta Assistant Examiner Richard L. Raymond Attorney-Oswald G. Hayes, Andrew L. Gaboriault, Mitchell G. Condos and Hastings S. Trigg s71 ABSTRACT Compound having the formula:

'acmc'ihcw" (nom -m-o on wherein R is alkyl (C,-C haloalkyl C C allcenyl' (C2C4), phenyl, 'alkylphenyl, or halophenyl, are new compounds that are useful as insecticides.

3 Claims, N0 Drawings l-(2-CYANOETI'IOXY)-2,Z-DICIILOROVINYL PHOSPHATE ESTERS BACKGROUND OF THE INVENTION 1. Field of the Invention This invention is directed to novel dichlorovinyl phosphates having a cyanoethoxy substituent and their use as insecticides.

2. DESCRIPTION OF THE PRIOR ART The compounds most closely related to the compounds of this invention are disclosed in U.S. Pat. No. 3,324,203 as nematocides. They have the formula:

wherein R is long chain alkyl. Insofar as is now known, the compounds of this invention have not been disclosed in the literature.

SUMMARY OF THE INVENTION This invention provides compounds having the formula:

oc rhdfizcN nohi -o-c CClz wherein R is alkyl(C,-C,), haloalkyl (C -C alkenyl (Cg-C phenyl, alkylphenyl, or halophenyl. It also provides their use in combatting insects and, insecticidal compositions comprising these compounds and a carrier therefor.

DESCRIPTION OF SPECIFIC EMBODIMENTS Non-limiting examples of the compounds of this invention are:

di-p-chlorophenyl l-( 2-cyanoethoxy)-2,2-

dichlorovinyl phosphate; di-m-bromophenyl dichlorovinyl phosphate;

l-(2-cyanoethoxy)-2,2-

ditolylphenyl l-( Z-cyanoethoxy )-2,2-dichlorovinyl phosphate; dixylylphenyl l-( Z-cyanoethoxy)-2,2-dichlorovinyl phosphate; and methyl p-nitrophenyl dichlorovinyl phosphate.

The compounds of thisinvention are readily prepared by reacting Z-cyanoethyl trichloroacetate l-( 2-cyanoethoxy)-2,2-

with a phosphite, e.g. trialkylphosphite, alkyl diarylphosphite, etc. These phosphites are prepared, as is well known in the art, by reacting phosphorus trichloride with the hydroxy derivative (e.g. an alcohol) of the desired ester substituent in the presence of a I-ICl acceptor, such'as pyridine or otherorganic base. The preparationof the compounds ofthisv invention is demonstrated in the-following illustrative examples.

EXAMPLE I Preparation of Z-Cyanoethyl Trichloroacetate EXAMPLE 2 Dimethyl l-(Z-Cyanoethoxy)-2,2-dichlorovinyl Phosphate The ester of Example 1 (4.3 g) was dissolved in benzene ml), and trimethyl phosphite (2.5 g) in benzene (10 ml) added. The resulting solution was refluxed overnight, then evaporated to give the product (5.2 g), for which the structure was confirmed by 'NMR [doublet at 6.1 'r, J=l2cps (POCHg), triplet at 7.18 '1', J% cps ,(OCI-LCILCN), triplet at 5.68 1-, J=6 cps (OCI'I,CI-I,CN')]. The integration of the NMR spectrum was commensurate with the assigned structure.

v EXAMPLE 3 Diethyl l-(-2-Cyanoethoxy)-2,2-dichlorovinyl r Phosphate v Thesame reaction as in Exam'p'Ie'Z, butjusing triethyl phosphite (3.3 g) in place of trimethy'l phosphite, gave the diethyl ester, for which the structure was confirmed by NMR [triplet at 8.61, J=7 cps (POCI-I,CH,), triplet at 7.l8 1-, J=6 cps (CILCN), multipletat 5.7 1-, P-

INSECTICIDE TESTING METHODS DIP TESTS I MEXICAN BEAN BEETLE Epilachna varivestis Mulsant( MB) Lima bean leaves of uniform size are momentarily dipped in a 500 ppm. water-acetone solution of the test compound. When dry, the treated leaf is placed in a screenedpetri dish and exposed to l O'fourth instar larvae. The percent mortality is recorded after 48 hours. Compounds that show percent or more mortality are retested at l00 and 10 ppm. TWO-SPOTTED SPIDER MITE Tetrany'chus telarius Linnaeus (SM) I I f Infested trifoliate bean leaves (Henderson bush lima) are selected that have as many as twenty adult mites per leaf. Leaves withm ites attached are momentarily dipped into a 500 ppm. emulsion, solution, or suspension of the testcompound and then placed (petiole only) in a 4 oz. bottle of water'for observation. Per cent mortality is observed after 72 hours. If 90-100 percent mortality'is. observed, compounds are retested at and 10 ppm.

HOUSEFLY Musca domestica Linnaeus (HF) Adult houseflies are contained in 100 mm. petri dish screened cages and exposed to a spray of ml. acetone solution of test compound. An initial concentration of 500 ppm is used, with 10 flies in each cage. Percent mortality is observed after 24 hours. When over 90 percent mortality is observed, the compound is retested at lower concentrations. GERMANCOCKROACH Blattella germanica Linnaeus (GC) This test is conducted in a manner similar to that used for the housefly. The test specimens are 10 cockroaches per screened petri dish.

BEAN APHID Aphis fabae (BA) This test is conducted in a manner similar to that used for the housefly. The test specimens are Nasturtium leaves infested with bean aphids.

BOLL WEEVIL Anthonomus Grandis (BW) This test is conducted in a manner similar to that used for the housefly. The test specimens are 10 boll weevils per screened petri dish. TWO-SPOTTED SPIDER MITE Systemic (S/SM) Young lima bean seedlings are placed in test tubes containing 50 ppm. solutions of test material. After 72 hours, mites are introduced by placing inverted miteinfested leaves on the test plants. Mortality is recorded 72 hours after the seedlings are mite infested. Compounds active at 50 ppm. are retested at lower concentrations of 10 and 1 ppm.

The compounds of Examples 2 and 3 were subjected to these insecticidal tests. The results (per cent control) are set forth in the Table.

TABLE Compound of Example 2 ppm MB SM H BA BW S/SM' GC 500 100 90 I00 0 100 90 30 30 9O 2O 80 lo 20 O 20 O 0 Compound of Example 3 ppm MB SM H BA 8! S/SM' GC 500 100 I00 l00 l00 90 60 l00 100 100 90 70 100 0 0 60 10 I00 40 Tested at 50 and 10 ppm.

Although the present invention has been described with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of this inwherein R is alkyl (C -C haloalkyl (C -C alkenyl (C C.,), phenyl, alkylphenyl, or h alophenyl.

2. A compound of claim 1, wherein said compound is dimethyl l-( Z-cyanoethoxy )-2,2-dichlorovinyl phosghate.

3. compound of claim 1, wherein said compound 18 diethyl phosphate.

'1 -(2-cyanoethoxy)-2,2-dichlorovinyl t I I i 

2. A compound of claim 1, wherein said compound is dimethyl 1-(2-cyanoethoxy)-2,2-dichlorovinyl phosphate.
 3. A compound of claim 1, wherein said compound is diethyl 1-(2-cyanoethoxy)-2,2-dichlorovinyl phosphate. 